DE2059864A1 - Process for the preservation of liquid food - Google Patents

Description

Ueno Fine Chemical Industries, Ltd., Osaka, Japan Process for preserving liquid food.

The invention "relates to a method for the preservation of liquids Food. In particular, the invention relates to a Process for preserving liquid food, which consists in adding a dihydroxybenzoic acid ester to the liquid food or adding a dihydroxyphenyl alkyl ketone and a composition of liquid food, which is stabilized against decomposition and putrefaction during storage.

The term "liquid food" as used herein Application and used in the claims means liquid condiments, such as soybean oil, vinegar and sauces and beverages, such as natural fruit juices, carbonated drinks, beer, fruit wine, wine and sake or rice wine.

Preservatives commonly found in liquid foods are used are benzoic acid, salicylic acid, dehydracetic acid salts, p-hydroxybenzoic acid esters and salts of sorbic acid.

With these preservatives it sometimes happens that one sufficient preservative effect is not achieved if they

20983070077

ORIGINAL INSPECTED

Added in amounts permitted by food laws. Furthermore, their effects depend on the species of the foods to which they are added.

For example, in the case of beer, heptyl p-hydroxybenzoate is used in an amount of 10 to 12 ppm and this amount is effective against the fouling microorganisms such as yeast and lactobacilli. Since heptyl p-hydroxybenzoate has only limited solubility in beer, it sometimes precipitates at temperatures around ⁰ ° C. and the beer becomes cloudy. In the case of soybean oil, the propyl and butyl esters of p-hydroxybenzoic acid are used to control putrefactive microorganisms such as wild yeast, but these esters are used in the case of soybean oil which is not heated ^{to 80 ° C. for 20 to 30 minutes} was decomposed by esterase remaining in soybean oil, and its effects are mendacious. In the case of rice wine, in Japan it is allowed to use silica in an amount up to 250 ppm in order to control the main putrefactive bacteria such as Lactobacillus homohiochi and hiochio-Lactobacilli, but addition of salicylic acid in such amounts does not give a sufficient preservative effect. Furthermore, in the case of salicylic acid, there is a problem of toxicity. Butyl p-hydroxybenzoate is mainly used as a preservative against the main putrefactive bacteria in vinegar, such as Acetobacter xylinum and other acetic acid bacteria. However, at a concentration effective to control such putrefactive bacteria, for example around 140 ppm, butyl p-hydroxybenzoate has a tendency to precipitate during storage at around ⁰ ° C. because it has limited solubility in vinegar and the vinegar becomes opaque and cloudy. When benzoic acid or sorbic acid is used to control the putrefactive microorganisms in fruit juices, such as yeast and mold, these acids adversely affect the smell and taste of the juices. When butyl p-hydroxybenzoate and sorbic acid are used as preservatives for rice wine or fruit wine , they have at their effective concentrations (70 to 100 ppm for the former and

20983Q / 0077

200 to 400 ppm "in the latter) has a very bad influence such drinks, with the result that the value of a drink is lost.

.It has now been found that aromatic carboxylic acid esters or aromatic ketones which contain two hydroxyl groups bound to a benzene nucleus ^ excellent antibacterial spectrum and have a very low toxicity as precursors of these compounds occur in nature and are generally harmless to the human body.

Furthermore, it has been found that these compounds have excellent solubility in liquid foods and that they are excellent Have storage stability.

The present invention relates to a method for preservation of liquid food, which is characterized in that a compound is a liquid food the formula:

(M0) n

COOR

COR

where η 2, R is an alkyl group having 3 to 8 carbon atoms and M is a hydrogen atom, an alkali metal or a half Moles of an alkaline earth metal mean.

• In the general formulas I and II, those expressed by R can be used Alkyl groups can be either straight chain or branched, but in general it is preferable that R is straight chain Is an alkyl group.

Compounds of the formulas I and II used in the present invention

2Ό 9-830 / 00 7 7

Findings that can be used are given in Table I.

Table I.

Connect Structural formula Solubility (// ml) 15 $ aq
solution
ν. Ethanol Melting point manure
No. HO- / V- COOC ₃ H ₇ 'Water 7.02 χ-10 ² ~ [Boiling point,
³ ( ⁰ C) 1 "-COOC ^ H ₉ 2.50 χ ΙΟ ² 5.13 χ ΙΟ ² 39 2 »-COOC ₅ Hh 1.08 χ ΙΟ ² 8.62 χ 10 60-61 3 -COOO ₆ H ₁₃ 5.88 χ 10 4.21 χ 10 [145 / 0.08 mmHg] U "-COOC ₇ Hi ₅ 1.37 χ 10 2.50 χ 10 [147 / 0.1 mmHg] * "-COOC ₈ Hi ₇ 5.82 1.61 χ 10 [156 / 0.1 mmHg] 6th 3.28 [160 / 0.2 mmHg]

20983 (1/0 0 77

: ^! '!'! '! ϋ ■ " ■: ■'-" »τ ■■ ■ ^{ιι | 1Μ} j . ( βΕ -COOC ^ H ₉ 1.57 3 cl03 - I. 5.a χ1θ3 • 2059864 HO - (
V-COQG ₃ H ₇
■ - ι ■ M -COOC ₅ H ₁₁ 60 7th It —- * -COOC ₆ H ₁₃ 7.53> C ΙΟ ² 1.35 χΙΟ ² It -COOG ₇ H ₁₅ 3.10 y : 10 ² 6.19 XlO ² 62-4 δ I ^η -COOCgH ₁₇ 1.91 a : 10 ² 5.72 XlO ² [145/1 mmHg] . 9 It 5.65 χ : .1Ο 1.13 χΙΟ ² [170/2 ramHg] 10 It V-CCOC ₃ H ₇
ZZJ 2.46 χ : 10 2.00 χΙΟ [168/1 mmHg] 11 HOs. -COOC4H9 [178/1 mmHg] 12th HO -ξ
-V = -COOC ₅ H ₁₁ 1.29 χ 1θ3 4.37 χ1θ3 13th Il -COOC ₆ H ₁₃ 5.45 χ ΙΟ ² 1.49 χ1θ3 115 It -COOG ₇ H ₁₅ 2.92 χ ΙΟ ² 7.80 χ ΙΟ ² 113-5 Π Il -COOCgH ₁₇ 1.81 χ ΙΟ ² 5.43 χ ΙΟ ² 93.5 «94.5 15th Il 7.20 χ 10 1.45 χ ΙΟ ² 117 16 Il VcOOC ₃ H ₇
ZZJ 1.91 χ 10 2.75 χ 10 84-86 17th HO 101-103 18th > -COOC ₁₄ H ₉ 1.86 χ 103 7.29 χ 1θ3 HO - (KX) C ₅ H ₁₁ . 60-61 19th It -COOC ₆ H ₁₃ 6.48 χ ίο ² 1.35 χ ΙΟ ³ η -COOC ₇ H ₁₅ 2.14 χ ίο ² 6.48 XlO ² [198 / 0.2 mmHg] 20th It -COOCgH ₁₇ 8.22 χ 10 4.87 χ ΙΟ ² [205 - ao
/O.I5 raraHg] 21 η 3.92 χ 10 1.20 XlO ² [208-212
/ OI mmHg] 22nd η 2.12 χ 10 6.88 ■ κ 10 [2I5 / O.I mmHg] 23 [22O / O.I raraHg] 24

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HO-Z ^ V-COC ₃ H ₇ 6th 3.20 χ ΙΟ ³ 20598R4 25th "- COC ^ H ₉ 1.53 χ ίο ³ 6.93 χ ΙΟ ² 52-4 26th "- COC ₅ H ₁₁ 3.94 χ ΙΟ ² 2.18 χ ΙΟ ² 57-60 27 "-COC ₆ H ₁₃ 5.68 χ 10 1.48 χ ΙΟ ² 53-5 28 "-COC ₇ H ₁₅ 2.50 χ 10 7.45 χ 10 44-47 29 DH
/ "V-COC ₃ H ₇
HfT 9.13 5.31 χ ΙΟ ² 62 - 63 30th "-COC4H9 2.61 χ ΙΟ ² 2.93 χ ΙΟ ² 79-82 31 "" COC ₅ H ₁₁ 7.44 χ 10 7.96 χ 10 51 - 4 ^! , 32 -COC ₆ H ₁₃ 3.74 χ 10 7.21 χ 10 77-9 33 "-COC ₇ H ₁₅ 1.89 χ 10 6.19 χ 10 88-90 34 HO.
HO - (^ V- COC ₃ H ₇ 1.32 χ 10 1.09 χ ΙΟ ³ 85-87 35 "-COC ₄ H ₉ 7.70 χ ΙΟ ² 9.46 χ ΙΟ ² 144-6 36 "-COC ₅ H ₁₁ 3.71 χ ΙΟ ² 5-58 χ ΙΟ ² 94-6 37 «-COC ₆ H ₁₃ 1.80 χ ΙΟ ² 1.49 χ ΙΟ ² 77-81 38 ". -COC ₇ H ₁₅ 3.66 χ 10 6.00 χ 10 83-85 39 3.30 χ 10 81-86

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In the present invention it is critical that the compound, expressed by Formula I or II has an alkyl group R "containing 3 to 8 carbon atoms. Among the compounds expressed by the formulas I and II are those that contain alkyl groups of up to 2 carbon atoms have as radical R, not suitable, since their antibacterial effect is very weak and their idoxicity is very high is high. On the other hand, compounds as a group R are a Containing an alkyl group having 9 or more carbon atoms are not preferred because of their poor solubility.

The hydroxybenzoic acid esters according to the invention or the dihydroxyphenyl alkyl ketones can be used in the form of a salt when the hydrogen atom is one or more hydroxyl groups replaced by an alkali metal such as sodium or potassium, or by an alkaline earth metal such as magnesium and calcium is. If the esters or ketones according to the invention are used as salts, their solubility in water is further improved.

All compounds of the formulas I and II used according to the invention are gentle in liquid foods soluble. Furthermore, the compounds according to the invention have a Structure similar to the structure of p-hydroxybenzoic acid ester is. The use of p-hydroxybenzoic acid ester is suggested by considered safe and harmless by the World Health Organization (WHO) and the Food and Agriculture Organization (FAO) man assumes that the course of the internal metabolism of the compounds according to the invention is similar to the metabolism of p-hydroxybenzoic acid ester is. Other compounds which are analogous to the compounds according to the invention, such as gallic acid, protocatechic acid and phloroglucinocarboxylic acid, are widespread in nature and their safety is very high.

The compounds according to the invention can be obtained from many liquid foods, such as liquid spices, for example soybean oil, Vinegar and sauces and for beverages, such as natural ones Fruit juices, carbonated drinks, beer,

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Wine, fruit wine, and sake, can be used, but they are special effective when used to preserve fermentation products such as vinegar, soybean oil and alcoholic beverages, be used.

When the above compounds are used on foods that are high in protein, they tend to stick to the proteins to become bound and lose their preservative properties. Accordingly, it does not make sense to use the inventive Use food preservation compounds that contain protein in large quantities.

The compounds of the invention exhibit high solubility in liquid foods and even when in relatively high solubility Concentrations, for example 300 ppm, are added, they do not fall out during storage. As the above connections generally having high antibacterial activity, sufficient effect can be obtained by adding them to liquid Adds food in amounts of 5 to 60 ppm.

In the practice of the present invention, the compounds of formulas I or II can be added at each stage in the preparation of the liquid food. You can in the form of an aqueous solution in alkali hydroxides, such as sodium hydroxide and potassium hydroxide, are added. You can too are added after one or two of their hydroxyl groups have been converted into the corresponding alkali metal salts. They can also be in the form of phosphoric acid esters or glycerol ethers or in the form of a solution in ethanol, propylene glycol or other edible harmless solvents such as glycerin and water can be added. For example, they can be in

a mixed solvent of propylene glycol and sodium hydroxide can be used.

The antibacterial activity of some compounds of the formulas I and II used in the present invention are given in Tables II and III. The numeric values that

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given in the tables are values of the minimum growth inhibition concentration obtained in antibacterial tests, the tests being carried out at 3O ⁰ O for 4 in a potato dextrose medium or in an agar medium and using various bacteria, yeasts and fungi.

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Table II

Bacterium -1 2. 3 · , ₇ . Compound (ί / ml) • 9 13th IA 15th 19th 20th 21 Staphylococcus aureüs 209P 100 100 25th AOO 8th 100 4.00 4-00 200 800 800 800 Bacillus subtilis PCI219 100 100 25th 4.00 AOO 50 AOO 4-00 100 AOO AOO AOO Salmonella enteritidis 1891 4.00 200 > 100 4.00 4.00 100 200 200 200 AOO ACO AOO Escherlchia coli 0-55 AOO 4-00 > 100 4-00 4.00 > 200 AOO 4.00 AOO 800 800 800 Protittfs vulgaris HX19 50 50 > 100 4.00 4-00 50 4-00 ■ 200 100 200 200 200 Aspergillus niger LAM3001 125 125 > 250 250 AOO 125 500 500 . 250 1000 1000 1000 Hhizopus nigricans I.AM6070 125 250 250 250 Saccharomyces cerevisiae 62.5 62.5 62.5 125 125 62.5 250 250 125 500 500 500 Hansenula anomala 62.5 62.5 > 250 125 125 £ 62.5 250 250 125 1000 1000 1000 Candida utilis 62.5 62.5 125 250 125 62.5 250 250 125 500 500 50th Q 250

ro ο to co .to

25th 26th Table III ν erDir
30th Läunä ο / π
3 ¹ il)
32 35 36 37 a
Bacterium 400 200 27 800 100 100 800 800 400 Staphylococus aureus 209p 400 200 100 400 100 100 800 800 800 Bacillus subtilis PCI219 400 100 50. 4OO > 200 _BC Λ..200 800 400 200 Salmonella enteritidis I89I 400 400 200 800 > 200 ^ 200 800 800 400 Sscherichia coli 0-55 200 100 > 200 400 100 100 800 400 200 Proteus vulgaris HXI9 25Ο 125: 25th > 25O 625 > 31.25 > ₅ 00 250 Aspergillus niger IAM3OOI 25Ο 125 125 > 250 31.25 > 31.25 > 500 500 250 Saccharomyces cerevisiae 250 125 <7.85 > 250 31.25 > 31.25 > 500 > 500 .250 Hansenula anomala > 250 125 31.25 > 250 31.25 > 31.25 > 500 500 250 Candida albicans ■ 31.25

In Tables II and III the numbers correspond to the compounds the numbers in Table I. These numbers are also used in the following tables.

In general, most have liquid foods a pH value of 2.0 to 5.0 and they contain certain amounts of organic acids, amino acids or saccharides. Accordingly they tend to be a culture medium for bacteria such as lactic acid bacteria, molds and film-forming yeasts result. When the above-mentioned compounds of formulas I and II to such liquid foods in the above Concentrations are added, so they show a better preservative effect compared to the usual preservatives. Furthermore, these compounds are not decomposed by the liquid food products, but increase the shelf life the food. Accordingly, the liquid foodstuffs in which the compounds according to the invention are incorporated were eaten without fear of their toxicity and their harmlessness and safety is much better, compared to known food preservatives.

The preservative effects and the antibacterial activities of the compounds according to the invention depend on the type of most putrefactive microorganisms of the corresponding liquid food and the position of the hydroxyl groups and the number of carbon atoms in the alkyl group and heavily on the type of food

which the connections are used. Accordingly, a suitable compound will be depending on the kind of the liquid Food to be preserved is selected.

For example, in the case of soybean oil, vinegar and fruit juices the number of carbon atoms of the alkyl groups is more important than the position of the hydroxyl groups and it is desirable to have one To use compound which has 3 to 5 carbon atoms in its alkyl part contains.

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To this day, butyl p-hydroxybenzoate is often used for soybean oil used as a preservative. However, this compound shows relatively little antibacterial activity and it is therefore required to use this compound at a concentration of 50 to 100 Y / ml. So it sometimes happens that a

that itself
fails and} at the viand of the soy bottle black

! Form opacities. In winter, the solubility of the compounds is often lowered below their effective concentration. Furthermore, if this preservative is added to soybean oil that has not been heated sufficiently or to raw soybean oil, it is decomposed by the esterase contained in the soybean oil and it is impossible to carry out pasteurization treatment that is suitable for the taste and On the other hand, it has been found that the dihydroxybenzoic acid alkyl ester of the present invention is sufficiently preserved at concentrations as low as 15-20% / ml soybean oil and that it overcomes the above disadvantages of the known preservatives. It has also been found that the addition of the inventive dihydroxybenzoic acid alkyl ester at a concentration of 10 to 20 tf / ml in sauces and stock liquids, for example for diluting soybeans or liquids containing amino acids, has excellent preservative effects, as in the case of the soybean oil itself.

The decomposition and putrefaction of vinegar are caused by acetic acid bacteria, v / ie Acetobacter xylinum and Acetobacter aceti, and a film is formed, cloudiness occurs and the acidity is lowered. The use of salicylic acid and p-hydroxybenzoic acid esters as preservatives for vinegar is allowed, but salicylic acid does not work at the allowed concentrations and p-hydroxybenzoic acid esters often precipitate at their effective concentrations (140 Jf / ml) in winter, making the vinegar cloudy. The compounds according to the invention prevent the decomposition and putrefaction of vinegar at concentrations of 20 to 30 W / ml and they overcome the above-mentioned drawbacks which the known preservatives for vinegar have.

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Soft drinks are divided into types that are carbonated and those that are non-carbonated. It is permitted to use benzoic acid (600 Ω / ml), dehydroacetic acid (50 ^ f / ml) and a p-hydroxybenzoic acid ester (100 Ω / ml) as preservatives for both types of soft drinks, even if these substances are added in permitted concentrations the formation of turbidity caused by yeast can often be observed. The compounds of the present invention prevent such decomposition from occurring at the concentration of 20 to 30 Jf / ml.

Natural fruit juices are easily spoiled by microorganisms in the course of pressing them until they are filled into cans or bottles, and such decomposition causes the appearance of cloudiness and gas formation through mold, yeast and acid-resistant lactic acid bacteria. Such decomposition can be avoided to some extent by adding benzoic acid at a concentration of 500 Ω / ml, but this preservative gives the juice a particularly unpleasant taste and therefore hardly acceptable results are obtained with this preservative. Dehydroacetic acid is unsuitable as a preservative for juice because it gradually decomposes in the juice and loses its activity, and therefore decomposition can easily occur when a juice bottle is opened after a long period of storage. If the compounds according to the invention of the formulas I or II are used as preservatives at a concentration of 10 to 50 μ / ml, the above-mentioned disadvantages of the known preservatives can be overcome.

Are the compounds of the invention used as preservatives used for rice wine, it is desirable that in the above-mentioned formulas I and II, the two hydroxyl groups on the benzene nucleus are bound in 2,4 or 3,4 divisions, and that the Alkyl group R has a chain length corresponding to 5 to 8 carbon atoms. Connections with these structural properties show excellent solubility, they are stable, and they have high antibacterial activity. Furthermore, they are

209830/0077

. - 15 -

for controlling hiochic43akteria in a wide range effective and they affect the taste and smell of rice wine not badly when used as preservatives for Rice wine can be used. Furthermore, they do not cause discoloration or not getting sick of rice wine, even for long periods Storage times. As shown in the examples, these compounds are against at a very low concentration typical hioehx bacteria are effective and they allow control of the whole range of hiochic bacteria present in a Brewery to be found. Complete control of hiochac bacteria can be achieved by using n-hexyl-1,4-dihydroxybenzoate as a preservative for rice wine, for example used at a concentration of 15 to 20 ppm. This proves that the compounds of the invention are superior to lysozyme are attracting great attention as a new preservative has since lysozyme against hi οchic bacteria of lactobacillus acidophillus type is not effective although it has the properties of rice wine does not have a negative effect and is therefore used as a preservative appeared promising.

The preservation of sake according to the present invention is classified into the following three methods. The first method is mainly designed to avoid decomposition during storage in the sank. Clear and translucent rice wine, which is obtained by removing impurities from raw rice wine, is ^{heated to about 55 °} C. and then stored in a tank. If this heat treatment is insufficient, various yeasts and hiochics bacteria remain in the rice wine, and decomposition is caused by these organisms. In order to avoid the occurrence of such decomposition, it is preferred to add a compound of the formula I or II in an amount of 5 to 200 ppm, whereby the growth during the usual storage time of microorganisms (at most 1 year) is prevented and thereby decomposition during the storage time does not occur and fungicidal effect can be observed, which brings with it an effective preservation.

2098 30/007 7

According to the second method, sake is prepared in which the preservation compound of formula I or II according to the above first method is incorporated, treated with active carbon or other suitable adsorbent prior to being shipped to essentially to remove any preservative compound from the rice wine. With this procedure it is possible if you are at works carefully in the subsequent stages, as in the case of bottling in bottles to make sake that is essentially free of all preservatives and none at all Contains hiochic bacteria.

The third method consists in adding a compound of formula I or II in the amount indicated above to rice wine, that had been treated with activated charcoal before being shipped. This procedure is used when there is a risk of that hiochi rot occurs even after bottling, in Bottles. If a rice wine bottle is corked by the consumer, the rice wine catches - especially in summer - which does not Preservative contains, within a short time, rot through hiochi. The third method is suitable to rot, caused by hiochi bacteria, after opening the Bottle to prevent.

If the present invention is used for the preservation of beer, it is desired that in the compounds of the general formulas I or II, the two hydroxyl groups are bonded to the benzene nucleus in the 2,4- or 3,4-positions and that the alkyl group R is a Has a length corresponding to 6 to 7 carbon atoms. Using these compounds, unpasteurized beer can be ^{preserved at O 0} O without the appearance of any turbidity, which is not possible in the case of heptyl p-hydroxybenzoate. By using the compounds described above, the lowering of the foam-retaining property of beer, as observed in the case of p-hydroxybenzoate, can be greatly reduced.

Results of the antibacterial tests of the previously

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Mentioned species against common microorganisms carried out using a potato dextrose medium (in the case of yeast and mold) or an agar medium (in the case of common bacteria) are given in Table IV. The numerical values in the table are values of the minimum growth inhibition concentration (^ / ml) if cultivation is carried out ^{at 3O 0 O for 4 days.}

Table IV

Bacteria species Connection 17 Connection 29 Saccharomyces cerevisiae 15.6 <7.81 Saccharomyces rouxii <3.91 <7.81 Asporgillus niger 62.5 62.5 Staphylococcus aureus 50 12th Bacillus subtilis 50 12th Proteus vulgaris '50 12th

The main antibacterial activities of other compounds are given in Table V.

Table V

Connection Mr. Yeast ' Lactic acid bacil 16 <7.81 - 62.5 250 11 3.91 - 31.25 <25 28 7.81-15.63 <50 % 3.91 - 15.63 25-50 U 7.81 - 125 <5

20 9830/0 07

The harmlessness and safety of these compounds is characterized in that, when administered orally to mice, almost all of them have an LD, - ₀ value of 3 to 6 g, and the compounds are therefore characterized by very low toxicities.

If the present invention is used to preserve beer, one obtains sufficient effects, regardless of the time when the compounds of the formulas I or II during the Beer manufacturing process are added. However, it is preferred to fill the compounds just before the beer is bottled will add.

The present invention is also effectively used for the preservation of fruit wines such as wine made from grapes. In general, aerobic bacteria, such as Mycoderma genus, form films in fruit wines, such as crying robbery. Acetobacter or Bacterium genus bacteria cause acetic acid contamination and Bacterium genus bacteria cause tartaric acid fermentation, mannitol fermentation, the formation of bitter substances, fatty acids and lactic acids during the manufacturing process or during bottling. This has a bad influence on the quality of the product in many cases. In the case of white wine in particular, the use of preservatives to control the quality of the product is essential. For this reason, it is recommended to use sulfurous acid at a concentration of 450 ο / ml or salicylic acid at a concentration of 250 // ml, but these preservatives bring the problem of toxicity and their effect is insufficient.

If the present invention is used for the preservation of fruit wine, excellent results can be obtained with the method according to the invention Preservation effects in comparison with the known preservation methods in which sulfuric acid is used will reach. Furthermore, it was surprisingly found that the taste or by the method according to the invention

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the smell of the wine cannot be adversely affected in any way.

The minimum Wachstumsinhibierungskonzentrationswerte (K / ml) of the compounds according to the invention is obtained when culture experiments with yeast and acetic acid bacteria at 3O ⁰ C for 20 performs days in wine!, Which one 10 ^ water was added are given in labelle YI. It can be seen from the results given in labeile VI that the compounds used in the present invention are particularly effective against remodeling and contamination by acetic acid.

! üabelle VI

link
Mr. yeast Acetic acid-
bacterium I.
link
Ur. yeast acetic acid
bacterium 26th . 7.81 25th 9 7.81 10 .27 3.91 25th 10 3.91 10 23 3.91 10 11 1.92 10 29 .1.95 5 12th 1.92 5 31 15.63 50 21 15.63 50 32 7.81 50 22nd 7.81 25 ' 33 7.81 25th 23 7.81 25th 34, 3.91 10 24 3.91 10 15th 31.26 .50 3 15.63 50 16 15.63 50 4th 7.81 25th 17th 7.81 25th 5 3.91 10 18th 7.81 25th 6th 3.91 10

The following examples illustrate the invention without, however, restricting it.

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example 1

Crude soybean oil, which was free of preservatives, was subjected to 30 minutes at 60 ° C or 80 ⁰ of a pasteurization treatment, and then the impurities were then removed. Each of the compounds listed in Table VII was added to 20 ml of a soybean oil sample so pasteurized. The sample to be examined was added in the form of a solution in 1 η aqueous sodium hydroxide at various concentrations in 10 parts from 3 '/ ml to 30 // ml. Each sample was infected with a loopful of film-forming yeast and then the samples were stored for 7 days at 30 ⁰ C and the growth of yeast was investigated. The results (minimum growth inhibiting concentration - // ml) are given in Table VII. In Table VII, the symbol "+" means that haze was observed in the sample of soybean oil.

Table VII

Granted Konser
processing agent Pasteurization at 60 ° ⁷ days pasteurization ⁷ days Comparison test,
nothing added 3 days + 3 days + Butyl para
hydro xybenzoate > 30 + 30th Connection 1 > 30 27 18th Connection 2 18th IS Connection 3 18th 27 Connection 8 24 27 (Connection 9 24 2Λ Connection 14 24 24 21

Example 2

A solution of the test compound listed in Table VIII in 1 η-aqueous sodium hydroxide became about 100 ml of vinegar, which

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was free of preservatives, are added and each sample was infected with a loopful of a liquid acting Saprogen-containing Bacteria, and stored ⁰ C for 20 Say at 3O. The occurrence of turbidity and the decrease in acid strength caused by yeast and acetic acid bacteria were examined. The results are given in Table VIII. In Table VIII, the acidity is indicated by expressing the amount (ml) of 0.1 η aqueous sodium hydroxide consumed to neutralize 10 g of the sample. The acidity of the vinegar at the time of adding the test compound was 4.21. The symbols "-" to "+++" mean the absence of turbidity and the degree of intensity of the turbidity.

Table VIII

Preservation
link Added
- Lot
UAD Cloudiness 20 days Acidity Rental agreement
search, nothing
admitted 10 days +++ 10 days 20 days Butyl para-
hydroxybene zoat
Il 50
140 ++ + bls ++
i
+ to + 3.44 3.02 Connection 1
Connection 2
Connection 3
Connection 4 30th
30th
30th
30th . · · + to +
±
. +
i to- + 4.20 3.70
4.18 3.85 IiIl 4.22 4.06
4.18 4.10
4.19 4.12
4.18 3.98

Similar connections were made with respect to other liquid condiments, such as sauces and stick liquids, and it was confirmed that that the compounds according to the invention have higher effects against putrefaction and decomposition, at concentrations of 30 yVml as p-hydroxybenzoic acid ester at one concentration from 100 to 200 J / ml.

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Example 3

A bottle of a beverage which contained no preservative but was carbonated was opened at ⁰ ° C. and the test compounds listed in Table IX in 1N aqueous sodium hydroxide solution were added to the open carbonated beverage (approximately 200 ml). Then the drink was infected with 1 ml of a liquid containing effective yeast (the number of yeast was about 10 per g), and then the bottle was closed with a cork. The bottle was ^{stored at 30 °} C. for 21 days and the occurrence of white cloudiness was examined. The results are given in Table IX. The symbols "-" to "+ -H-" mean the absence of turbidity and the degree of intensity of the turbidity.

Table IX

Conservation
middle Granted
lot
(ό / ml) white haze ¹ ^ days ²¹ days Comparative experiment
nothing added ⁷ days ++ · +++ Benzoic acid
Dehydroacetic acid
Butyl para
hydro xyben zo at 600
50
.70 + + to +
+ to +
+ + bds ++
+ Us ++
•
-H-' Connection 8
Connection 9 30th
30th Kf I I; - ± bjs +
± to + -

From the results given in Table VIII it can be seen that the compounds according to the invention, compared with the known Preservatives such as benzoic acid, dehydracetic acid and p-hydroxybenzoic acid esters are much more effective at inhibiting the growth of yeast and) prevent the appearance of white turbidity in carbonated beverages.

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There have been similar investigations regarding "non-carbonaceous Drinks carried out, it was confirmed that the invention Terbindungen deliver excellent preservation results.

Example 4

A platinum loop full of an external bacterial liquid (containing active yeast, mold, acid-resistant lactic acid bacteria and other bacteria) was added to 50 ml of fruit juice made by squeezing an orange (Onshyu quality), and then added sugar in such an amount that a sugar content of 10 ^ was obtained. To the juice a solution of the compound indicated in table X in 1 η-aqueous sodium hydroxide was then added and the juice was kept at 3O ⁰ G ". The growth of molds and the appearance of turbidity in the juice was examined. The results are in Table X. The symbols "-" to "+++++" appearing in "" of the table mean the absence of mold or turbidity and the degree of intensity of mold growth or

the cloudiness in the juice.

j.aDej.je JL

Conservation
material Granted
lot "Cloudiness 7 days 10 days Mold growth 7 days 10 days Comparison
attempt,
nothing to-
• given ···
Benzoic acid 3 days ++
± to + +++ 3 days -to + Butyl- para-
hydroxy
benzoate 3,500 - -are you - - Connection 2
Connection 3
Connection 9
Link 1 30th - -until*
-to ± ir to +
I.
i - ±
-to i 30th
30th
30th
5 30 ι ι ι ι I I Il

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Example 5

Raw soybean oil free of preservatives was ^{pasteurized for 30 minutes "at 60 °} C. or 80 ^° C., and then the impurities were removed. Each of the compounds listed in Table XI was added to 20 ml of a pasteurized sample of soybean oil. The compound to be tested was added in the form of a solution in 1η aqueous sodium hydroxide at concentrations varying in 10 parts from 3 (T / ml to 30 tf / ml. A platinum loop of fully active film-forming yeast was added to each sample and then the sample was kept during 7 days at 30 ⁰ C and the growth of yeasts was studied the results (minimum Growth inhibitory concentration - tf / ml).. are given in Table XI compound a is an ethyl ketone, corresponding to compound 25, compound B is a hexyl ketone which corresponds to compound 25, compound C. is an ethyl ketone which corresponds to compound 30 and the Ve Bond D is a hexyl ketone which corresponds to compound 30. The symbol "+" in the table means that turbidity occurred in the simple soybean oil sample.

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2053864

- 25 slats XI

Preservative 60 ⁰ C pasteurization 7 days 5 80 ⁰ C Pas 3teurisierui Comparative experiment
nothing admitted 3 days + 3 days • 7 days Butyl para-
hydroxybene zoat + > 30 + + Connection A > 30 21 27 30th Connection 25 IS 15th 18th 21 Connection 26 12th 15th 15th 15th Connection 27 12th 12th 15th Connection B .12 TA 12th 15th Compound C 24- > 30 > 30 :> 3o Connection 32 > 30 15th > 30 > 30 Connection 'D 12th > 30 12th 15th > 30 > 30 > 30

Example 6

A solution of the compound indicated in Table XII in 1 N-aqueous Fatriumhydroxyd was added to about 100 ml of ethyl, which contained no preservatives and the ethyl sample was contained with a loopful of a putrefactive bacteria liquid active Saprogenusbacteria infected and for 30 days at 30 ⁰ C kept. The occurrence of cloudiness and the decrease in acidity caused by acetic acid bacteria and yeasts were investigated. The results are given in Table XII. In the table, the acid content is given in the form of the amount (ml) of 0.1 η-aqueous sodium hydroxide which is consumed to neutralize 10 g of the sample. The acidity of the vinegar at the time of adding the test compound was 4.21. The symbols "-" to "+++" mean the absence of turbidity and the degree of intensity of the turbidity.

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- 26 Table XII

Preservation
material Granted
lot
'(V / ml) Cloudiness 20 days Acidity 20 days Comparison ver
search, nothing .--
admitted 10 days +++ 10 days 3.02 Butyl para-
hydro xyben zo a t < 50 ++ + to-H- 3.44 3.70 . '■ "■" 140 - ± to + 4.20 3.85 Connection 25 30th - ± bjs + 4.18 4.01 Connection 26 30th - 4.19 4.17 Connection 27 30th - - 4.1S 4.19 Connection B 30th - ± to + 4.20 4.10 Connection 31 30th - ± 4.23 4.12 Connection 32 30th - ± 4.19 4.11 Connection 36 30th - ± 4.22 4.08 Connection 37 30th - -to + 4.19 4.16 - 4.18

Similar studies have been carried out with other liquid condiments, such as sauces and stick liquids, and it has been confirmed that that 2,4-dihydroxyphenylalkyl ketones, which act as an alkyl group R in formula II contain a butyl or pentyl group, better effect in preserving against rot and decomposition at concentrations of 30 // ml, compared with butyl hydroxybenzoate at a concentration of 100 to 200

Example 7

A bottle of preservative-free carbonated drink ^{kept at 0} ° C was uncorked and a solution of the test compounds listed in Table XIII in 1η aqueous nytrium hydroxide was added to the open carbonated drink (approximately 200 ml). The GE-

209830/0077

The potion was infected with 1 ml of a liquid containing active yeast (the number of yeast was about 10 ⁵ per g) and then the bottle was closed with a cork. The bottle was stored at 3O ⁰ C for 21 days and the appearance of turbidity was investigated. The results are given in Table XIII. The symbols "-" to "+++" mean the absence of turbidity and the degree of intensity of the turbidity.

Table XIII

Preservation
material Granted
Lot . .
ftf / ml) white haze 14 days 21 days Comparison ver
search, nothing 7 days «. Benzoic acid
Dehydroacetic acid
Butyl para-hydroxy
■ benzoate 600
50
70 ■ + + to +
+ to *
I. + to ++
+ to ++ Para-hydroxyphenyl -
butyl-ketone ■ 30 1+ II. ' ■ ± Connection 26
Connection 27 30 ·
30th - - * -

From the results given in Table XIII it can be seen that the compounds used in the present invention become essential in inhibiting yeast growth are more effective and that they prevent the occurrence of cloudiness in the carbonated drink compared to the known ones Preservatives, such as with benzoic acid, dehydroacetic acid and p-hydroxybenzoic acid esters.

Similar experiments were carried out on non-carbonated beverages, and it was confirmed that the

2 0 9830/0077

Compounds according to the invention have excellent preservation results deliver.

Example 8

A platinum loop full of putrefactive bacteria liquid (containing active yeast molds, acid-resistant lactic acid bacteria and other bacteria) was added to 50 ml of fruit juice obtained by squeezing an orange (Onshyu quality) and adding sugar in an amount up to a sugar content of 10 #. Then, a solution of the compound indicated in Table 1 in XIY η-aqueous sodium hydroxide was added to the juice and the juice was kept at 3O ⁰ C. The growth of mold and the occurrence of cloudiness were examined. The results are given in Table XIV. The symbols n_n _to n ₊₊₊₊₊ ii _} which appear in the table mean the absence of seed mold growth or of turbidity and. the degree of intensity of mold growth or cloudiness in the juice sample,

Table XIV

Admitted
level
lot Cloudiness 7 days 10 days Mold growth 7 days l ° days _| Preservation
rungsstoffi ^ 3 days -H- 3 days +++ III .1 I
TTTTT Comparison
attempt,
Benzoic acid 500 ± to + -H- ⁺ Butyl para-
hydroxy-.
benzoate 30th - - -to ± - - Connection 2
Connection 2 ¹
Connection 3 ' i 30
' 150 - - ί
t
t - - -to i . -

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■ ■ - 29 - *

From the results given in table XIT it can be seen that that the compounds according to the invention are very effective in order to inhibit the growth of mold and to prevent

TO

preventing cloudiness in the fruit juice / compared to benzoic acid.

Example 9

An alcoholic solution of a compound shown in Table XV was added to a rice wine peptone medium. The content of the compound in the alcoholic solution was less than $ 1. V / ater was then added to the medium to adjust the alcohol concentration to 1336. Each of the following four bacteria, which are often used as standard hioohij bacteria in experiments, were separately added to the medium in an amount of 10 cells per ml. The medium was stored at 3O ⁰ C and after 20 days of culturing, the minimum Yfachstumsinhibierungskonzentration (X / ml) was determined. For comparison, similar experiments were carried out using salicylic acid; and lysozyme carried out. The results obtained are shown in Table XV.

Used hiochig - bacteria

! lactobacillus homohiochi (E 42)

lactobacillus heterohiochi (fit)

Lactobacillus fermentum (H 34) Jj

Lactobacillus acidophilus (H?)

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205986A

- 30 Table XV

Conservation Minimum growth inhibition concentration (# 7 Lactobacillus
heterochiochi Lactobacillus
reimenturn Lactobacillus
acidophilus material Lactobacillus
homohiochi 200 200 400 Salicylic acid 4OC 10 <C 1 > 100 Lysocyra 20th 75 100 100 Connection 26 100 50 50 50 Connection 27 50 10. 25th 25th Connection 28 25th 10 10 10 Connection 29 10 100 100 100 Connection 31 100 50 50 50 Connection 32 50 10 25th 25th Connection 33 25th 10 10 10 Connection 34 10 100 50 50 Connection 38 100

Example 10

A rice wine, the preservatives contained and had an alcohol concentration of 16.0 fi, was infected with 2 ¹ X 10 ^"3 cells per ml of hiochJc lactobacilli which had been obtained in a brewery in Nada, Kobe, Japan. For the infected rice wine was added to a solution of a compound given in Table XVI in alcohol, at the concentration given in Table XVI. By adding water, the increase in the alcohol content in the sample, which was caused by the addition of the alcoholic solution of the preservative, was recorded the original concentration was set and then the sample was filled into blue glass bottles and the bottle was closed with a cork.For comparison, similar tests were carried out using lysozyme with 40 JVmI and using SaIi-

209830/0077

- 31 cylic acid carried out.

The bottle was then stored at 3O ⁰ G and the occurrence of turbidity, caused by hiochic bacteria was examined. The results are given in Table XVI. In Table XVI, the symbol "+" means that putrefaction occurred by hiochic bacteria and the symbol "-" means that putrefaction caused by hiochic bacteria was not observed. In the table, "white haze" means that white haze caused by precipitation of crystals occurred when the sample was ^{kept at 0} ° C. for 4-8 hours low, concentrations have excellent activity to prevent the "growth of hiochic bacteria and that they are much more effective than salicylic acid when used at a concentration of 500 ppm. This concentration is twice the allowable upper limit of the Salicylic acid concentration.

209830/0077

- 32 Table XVI

Conservation
material Trains
added
Lot -
C / ml) Storage time V days Π days 121 days 70 days Storage at
O ⁰ C during
48 hours Comparison ver
search, nothing
admitted + + + Salicylic acid
η 500
250 + + +
+ Lysozyme 40 + + + + Connection 28
ti 50
25th
10 - - - ■ + white haze Connection 34
ti
Il 25th
10
5 - - - + white haze

Were samples from rice wine containing the compounds of the invention incorporated in concentrations enthielteryiie over the effective Concentrations were, i.e., samples containing 50 ^ ml of the compound 28 or 25 / ml of the compound 34 contained, examined for taste before infection with h.iochJc bacteria, so found it was found that the addition of these compounds did not affect the taste or smell of the rice wine in any way. Samples into the the above compounds were incorporated above the effective concentration, showed no visible changes, such as a color change, even after being stored for 70 days.

Example 11

A commercially available rice wine that is free from preservatives

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- ■ 33 -

was substances, was separately prepared with TO fo Koji, mixed and then stirred to "at 30 ⁰ C for 4 hours and-filtered. To the Piltrat alcohol was added to the alcohol concentration to 20 ° set. To the medium was active carbon added ppm in an amount of 200, then the medium was filtered and kept in a water bath at 56 ⁰ C for 20 minutes, with the medium in a reaction vessel was containing a reflux condenser. then, the medium with 1.2 was χ 10 ² Cells infected or infected per ml hiochio bacteria that had been collected in a brewery in jffada, Kobe, Japan, and alcoholic solutions of the compounds 28 or 34 were added to the infected sample ppm or 10 ppm. For comparison purposes, salicylic acid was added at concentrations of 250 ppm and 500 ppm. The increased alcohol content caused by the addition of the preservative solution was conditional, was reduced to 20 ° by adding water. Each sample was transferred to a 200 ml beaker and sealed with a polyethylene film. In this state, the samples were ^{stored at 30 °} C. and then the state of the sample was examined. The results are given in Table XVII.

Table XVII

Preservation
material [Admittedly
lot
(// ml) storage time 7 days U days 21 days 70 days Comparison ver
search, nothing
• added · ·
Salicylic acid
It 250
500 + +
+ + '
+ +
+ Connection 28
Connection 34 25th
10 - - - - -

209830/0077

In Table XVII "the symbol" - "means that no hiochi rot and the symbol "+" means hiochi rot was observed.

Was the above experiment with hiochi putrefaction bacteria in one passport carried out, the sample showed the salicylic acid with a Concentration of 250 d / ml contained, hiochi rot.

After storage for 70 days, each sample of rice wine containing 400 ppm active carbon was mixed and filtered. The filtrate was then diluted with pasteurized water so that the alcohol concentration was 16%. The sample was then carefully into a pasteurized bottle crowded and the bottle was sealed with a cork and stored at ⁰ C 3O. The results are shown in Table XVIII, where the symbol "-" means that no hiochi rot was observed and the symbol "+" means that hiochi rot was observed.

Table XVIII

Conservation E.
material ^ Granted
"" Amount (/ ml) Storage time H days 21 days, 7 ° days + + Salicylic acid
Connection 28
Connection 34 500
25th
10 7 days - -

The amount of preservative remaining in the samples was determined by ultraviolet absorption analysis. The results are given in Table XIX. In the samples that had been treated with active carbon, the alcohol content, which had been lowered by evaporation of water, set again.

209830/0077

- 55 - 2059864 after To- After turning 70 hcUidlnn.p with Table XIX 100
100 had _lG0
100 active Kohler
70
■ <1 100 100 <1 Conservation
material Remaining preservative ratio
-T ₁ -S _n 7 Ο * \ Salicylic acid
(May be*/**)
Connection 28 " ¹ Hi ¹ D \)
Just Connection 54

Example 12

20 ltr. Mirin (sweet rice wine), which contained 17 # alcohol, 0.01 $ acids (identified as lactic acid) and 41 »2 fo sugar, were in four samples with 5 ltr. divided. Compounds 28 and 34 were added to two samples in concentrations of 25 μl and 10 μ / ml. For comparison purposes, salicylic acid was added to another sample at a concentration of $ 250 / ml. The compounds were added in the form of alcoholic solutions. The increase in alcohol content was regulated by adding water. Each sample was dispensed into 25 200 ml bottles and a platinum loop full of active Lactobacillus acidophilus was added to each bottle, then the bottle was closed with a cork. Each bottle was ^{stored at 50 °} C. and the condition of the sample was examined. The samples which had incorporated compounds 28 and 34 according to the invention showed no changes after 3 months. But all samples that contained salicylic acid were rotten within 50 layers.

Example 13

Experiments were carried out in a (lever piece) rice wine peptone culture medium carried out during 20 days in the same way as in Example 9, but using the dihydroxybenzene given in Table XX acid ester used. The results (minimum growth inhibition concentration - ^ / ml) are given in table XX.

209830/0077

- 36 Table XX

Preservation: 3-Minimum Growth Inhibition Concentration ( Lactobacillus
heterohiochi Lactobacillus
remote turn Lactobacillus
acidophilus material Lactobacillus
homohiochi 200 200 400 ^ Salicylic Acid 400 10 <1 > 100 Lysocyra 20th 150 200 200 Terbind. 15 200 75 100 100 »16 100 20th 30th 30th Ii γι 30th 10 10 10 ¹¹ 18 10 25O 25O 250 »9 300 100 100 I50 "10 150 25 ' 25th 25th "11. 25th 10 10 10 12th 10 200 200 Λ00 II 21 400 100 300 100 »22 300 50 50 200 μ 23 200 30th 30th 50 η 24 50 45 45 50 it 3 60 15th 15th 18th “ K 20th 5 <5 <5 Il 5 8th <C5 <5 <5 <5

Example 14

Rice wine, which was free of preservatives and an alcohol content of 16 had io, was infected with 2 χ 10 * cells per ml Hiochi bacteria and then filled into a 300 ml blue glass bottle. The compound indicated in Table XXI was added to the bottle in the amounts also indicated in the table; salicylic acid was also investigated for comparison purposes.

20983Q / 0077

The bottles were closed with corks and stored at 30 °. The appearance of turbidity caused by hiochi bacteria was tested. The results are shown in Table XXI, where the symbol "-" means no haze observed and the symbol "+" means that haze was observed. Each preservative was in porm an alcoholic Solution added and the increase in alcohol content due to the addition of the preservative was on the original Alcohol content of 16 ^ adjusted by adding water.

Table XXI

Conservation Admitted Storage time : - U days 21 day 70 days Storage at • · • • solution substance level
Me.ngß, 7 days ^; - + +
+ + O ^ ö during Comparative
search, not *
Salicylic acid (/ ml)
500 + - + + + Il 250 ■ - - ■ M - rerbind. 17 ' 50 - - white haze Il 30th + +. H 20th - - ■ - ^r erbind. 11 50 - - - white haze Il 25th - + • Il ' 10 - - - erbind. 4 20th - em - Il 10 - - ..K- 5

209830/0077

Were samples containing the above compounds in concentrations were incorporated which were above the effective concentrations, examined for taste, it was found that these compounds did not have a bad effect on the taste or smell of the rice wine. In all samples that the invention Containing compounds, no color change was observed even after storage for 70 days.

Example 15

20 ltr. Mirin (sweet rice wine), which contained 17.0 $> alcohol, 0.01% acids (determined as lactic acid) and 41.2 $ sugar, was divided into four parts of 5 liters each. divided. Compounds 17, 11 and 5 were added to the three parts in alcoholic solution in concentrations of 30 ^ / ml, 25 <f / ml and 5 JVmI. The remaining one part was examined as a comparative sample without preservative. Each compound was added in the form of an ethanolic solution and the increase in alcohol content due to the addition of the preservative was compensated for by adding water to the original alcohol content of 17 °. Each portion was filled into 25 200 ml bottles and each bottle was infected with a platinum loop of fully active Lactobacillus acidophilus. Then each bottle was kept at 30 ° C and the condition of the sample was examined. The samples which contained the compounds according to the invention were still unchanged after 3 months, whereas all comparison samples were moldy within 10 to 20 days.

Example 16

Saccharomyces cerevisiae, Saccharomyces ubarum and Lactobacillus pastorianus, known as putrefactive bacteria for beer, were grown separately in a 3% malt extract broth containing 4% ethanol. Using these broths, the antibacterial activities of compounds 17, 29, 16 and 28 were examined. A drop of the liquid in which 3 strains had been cultured for 24 hours was added by an injector to a medium containing the preservative compound.

209830/0077

held, and then incubated at 30 ⁰ G for 70 days and checked the growth of the bacterial samples. The minimum growth inhibition concentration (<^ / ml) was determined for each compound. For comparison purposes, n-heptyl p-hydroxybenzoate (POEH) was tested in a similar manner. The results are given in Table XXII.

Table XXII

Preservation
material Minimal growth inhibition concentration
(JT / ml) Saceharomyces
ttbarum Lactobacillus
pastorianus Connection 17
"Connection 29
Connection 16
Connection 28
K) bra Saceharomyces
cerevisiae 9
6th
12th
8th
8th 9
Λ
10
8th
6th 9
12th
8th
8th

Example 17

The preservative effects of compounds 17 and 29 on beer were examined. 1 ml of a solution of compound 17 or 29 in ethanol was added to 349 ml of unpasteurized beer and then the sample was stored in bottles at room temperature. Samples which contained POBH incorporated in a similar manner and a beer sample which had been pasteurized by heating were examined at the same time as comparisons. Wax storage at room temperature, a portion of the beer sample at O ⁰ C was kept for 2 weeks and then the solubility and stability of the preservative compound at O ⁰ G was examined. The results are given in Table XXIII, the "Storage" column showing the results obtained on storage at room temperature and the "Stability" column showing the results of the stability test at ⁰ ° C. In the table, the numeric values show the number of months

830/0077

during which the sample was stored without mold formation and the symbol "+" means that the appearance of white turbidity or a precipitate of crystals was observed.

Table XXIII

Concentrate. Compound I ⁷ ·' Rod*.'"* - Connection ^? Rod. ' POBH Lay. Rod. ( δ / ml) storage - - Lay. U ± not treated
deleterious
concurrently
8th (D
.ch
4th - 6th ± > 6 + 10 > 6 > 6 + > 6 + 12th > 6 > 6 H > 6

The samples containing compounds 17 and 29 incorporated at concentrations of 10 <17 ml or more were found to be excellently preserved, in a manner similar to the control sample which was pasteurized by heating. In the samples containing the compounds 17 or 29, ^{no white turbidity or precipitated crystals were found at O 0} C, at a concentration of 8 J / ml, while in the POBH sample at a concentration of 8 <^ / ml of white turbidity occurred. In the case of compound 17, no turbidity was observed even at a concentration of H // ml and is from this. it can be seen that the compound 17 is particularly excellent in terms of its solubility and stability.

Example 18

In this example the influence of the compounds 17 and 29 on the taste of beer is examined. Sample A was made by adding an ethanol solution of compound 17 or 29 to unpasteurized beer (the ethanol content was

209830/0077

about $ 0.3 billed on the beer), being a beer solution which contained the compound at a concentration of 10 // ml. Sample B was made by not too pasteurized beer added the same amount of ethanol as above (the ethanol content was approximately $ 0.3). Sample G was made, by adding ethanol in the same amount as above to beer that had been heat pasteurized "

A group of 10 experts was selected for the taste test, and pair tests of Samples A and B and Samples A and C were repeated twice. The temperature of the beer at the time of drinking was 6 to 9 ^° C. The results of the investigation are given in Table XXIV, with the symbol "*" indicating a clear difference of 5%.

Table XXIV

link number 17th Connection 29 number 4th number d. Check number Number number d. auditor d. Check fer, d d.Prü- d.Prü the C fer, Thief fer, fer, fer, essential the A essential the C the A the B better than as we lich essential essential A judge sent better lich lich borrowed th lich as a better better better better beur as a as B as A as B part beur ο. C beur- ο C be th part judge verdict th shared th th comparison d. rehearse 11 A and B 9 10 10 comparison d. rehearse A and C 15 * 5 16 *

From the results shown in Table XXIV it can be seen that the taste of the samples containing the compounds 17 and 29 was not spoiled in comparison with unpasteurized beer, and that they were judged much better,

209830/0077

than beer that has been pasteurized by heating.

Example 19

An ethanol solution of given in Table XXV preservative was added to red wine, which contained no preservative and then the wine was in each case inoculated with a loopful of film-forming yeast and acetic acid bacteria and stored for 70 days at 30 ⁰ C. The change in the quality of the wine was examined. No decomposition could be found in any of the samples, which was recognizable by the taste or smell after the preservative had been added. Furthermore, no color change was observed in any of the samples after 70 days of storage. The results of the preservation tests are shown in Table XXV ", where the symbol" + "means that white turbidity caused by the growth of microorganisms was observed.

Table XXY

Conservation
material Granted Storage time 14 days ²¹ day-f » ⁷⁰ days Salicylic acid 250 ⁷ days - + SO ₂ Λ00 - - · + + Connection 28
Connection 17
Connection 6 25th
30th
5 - - - -

Example 20

An ethanol solution of the preservative given in Table XXVI was added to white wine that did not contain a preservative, and then the wine became film-forming with active Yeast and acetic acid bacteria infected (where the

209830/0077

Degree of contamination of bacteria 2 χ 10 cells per ml) and were then bottled subsamples were stored at about 30 ⁰ C. The difference in quality was checked. No odor contamination was found in any sample after the preservatives were added
no color change was found in any sample,
after the sample was stored for 70 days. The results of the preservation tests are given in Table XXVI, where the symbol "+" means that white turbidity occurs due to the growth of microorganisms.

• Table XXVI

Preservation
material Granted
lot
(i / ml) Storage time 7 days - 14 days 21 days 70 days Salicylic acid 250 to - - + + SO ₂ 400 - - - + + Connection "28 25th + - - mm Connection 17 30th - - - Connection 6
no additive
Equalization
y ouch 5 + + +

209830/0077

Claims (5)

- 44 claims 1. A method for the preservation of liquid food, characterized in that the liquid food a compound of the formula (MO) _{n. k} (M0) n. -COOR or Λ- V-COR H wherein η 2, R denotes an alkyl group having 3 "to 8 carbon atoms and M denotes a hydrogen atom, an alkali metal or 1/2 mole of an alkaline earth metal", in an amount of 5 to 300 ppm. 2. The method according to claim 1, characterized in that the compound is added in an amount of 5 to 60 ppm. 3. The method according to claim 1, characterized in that the compound is in the form of a solution in an edible safe Solvent is added. 4. The method according to claim 1, characterized in that the liquid food is soybean oil and that R in the formula represents an alleyl group having 3 to 5 alkyl groups. 5. The method according to claim 1, characterized in that the liquid food is rice wine and that the compound which is added is expressed by the formula: ( _{M0) n} V-COOR ¹ or. ^, \ y_coR- ¹ 209830/0077 - 45- Ii wßi TL (have the meaning given above ,, R an Al m # for 5 · b & S / $ carbon at cimen; means, imä where in 2. ». Φ or 5,, 4 positions ztt ΟΘΟΒ; odi & r GO ^ are bound. β «· method according to iasprmch 1, characterized in that the liquid lfaä3? -iBgsiaittel eggs and that is the compound that is added, is expressed by the formula: or ^^ Vcor2 ο where M and 'η. have the meanings given above, R a alkyl group. having 6 to 7 carbon atoms means, and wherein two MQ groups on the benzene nucleus in 2,4 or 3 * 4 positions 2? ·
to the. Groups GOOR or GOR are bound.